Applicability of the quantum-chemical calculations of potential and electrooptical function parameters to the standardless spectrum analysis of heteroatomic organic compounds

The quantum-chemical calculation of potential and electrooptical function parameters for 32 heteroatomic (nitrogen-, oxygen-, and sulfur-containing) compounds was performed with the use of the B3LYP/6-311G(3df,3pd) basis set. With the use of a small correction of the potential function with unified scaling factors, the calculated frequencies and absolute intensities of fundamental absorption bands agreed satisfactorily with the experimental values. The average and standard deviations of calculated and experimental frequencies were no higher than the half widths of their absorption bands. The results suggest the applicability of these calculations to the standardless spectrum analysis of gas mixtures.